Naphthazarine intermediate-aro



Patented Nov. 1, 1938 NAPHTHAZARINE INTERMEDIATE-ARO- MATIG AMINE CONDENSATION PROD- UCTS John M. Tinker, Benns Grove, and Louis Spiegler, Woodbury, N. J., and David X. Klein, Milwaukee, Wis., assignors to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application April 29, 1937, Serial No. 139,730

Claims. (Cl. 260-56) 5 reduced in sulfuric acid a compound generally It is therefore an object of this invention to 5 referred to as naphthazarine intermediate, p epare new a d u l po ds of t e i having the probable f rmula naphthalene series by controlled condensation of l O NHZ naphthazarine intermediate with arylamines. 2 II I It is a further object of the invention to prepare new and valuable dyestuffs which have good. 10

affinity for cellulose acetate and which dye that and related materials in blue to greenish blue shades.

L 0H It is a still furtltier object of the inventionto dye cellulose aceta e and related materials with 15 produce? and t comtfimnd can be cor;- dye preparations comprising the mono molecular ensed with ammes furt er sulfonated O condensation products of naphthazarine interproduce dyestuffs. It is also known that in the formation of this naphthazarine intermediate medlate Wlth arylammes' b th d t d d In preparing these new compounds, the naphi t 8 pro no is qul e eas y re 9 an thazarine intermediate is dissolved in acetic acid 20 closely related Compounds havmg the and substantially molecular amounts of the arylfouowmg probable formulas amine are added. The mass is heated for a few 0 NH H0 minutes to temperatures of from about 90 C. to I H the boiling point of the mass and then cooled and any insoluble residue is filtered ofl". On

and drowning the filtrate in water the dyestufi precipitates out. ii i The following examples are given to more fully EN 0 N32 011 illustrate a preferred method for preparing these are also formed. All three of these compounds new compoun s- The parts used e by Weight 30 may invariably be present in the crude naphtha- Example 1 zarine intermediate product. The naphthazarine intermediate, however, may be obtained in'sub- Parts Of naphthazarine intermediate are stantiaiiy pure f m by recrystallization f m dissolved in 200 parts of glacial acetic acid. 5.4

acetic acid or by oxidation or reduction and fi1terparts of lfl-phenylene diamine e added and the 35 ing the reduced or oxidized material to free from mlxture heated fifteen mmutes at insoluble impurities and then re-oxidizing or re- After coolmgi crystals of a small amount of ducing back t0 the intermediate ail f which soluble material are filtered off and the filtrate is known in the prior art drowned in 2000 parts of water. The precipitate 40 It has been found that whilethe condensation formed is filtered Washed until the washiings 40 products obtained by condensing naphthazarine assume a pale greemsh blue color. and then fined. intermediate with amines, as more fully described The bluemlack Powder When Suspended 111 an in U. s. Patent 647,370, or by condensing the sulaqueous dye bath containing soap dyes cellulose fonated product described in U. S. Patent 627,896 acetate in bright blue Shades Of C e t l ht with amines by the process described in U. S. fastnessv45 Patent 646,796, are suitable for coloring oils, fats x ple 2 7 and waxes, including petroleum oil fractions such 10 parts of naphthazarine intermediate are 7 as gasoline, in blue to grefln Shades, and when solved in 200 parts of glacial acetic acid and 5.5 Sulfonated are useful as acld W001 dyestuffsi they parts of p-aminophenol are added to the solution. have practically no fini y f Cellulose acetate The solution is boiled three-fourths of an hour 50 We have f however, that Where the C011- and cooled. A small amount of precipitate is fildensation of the arylamine with the naphthatered off and the filtrate poured into 2000 parts zarine intermediate is carefully controlled whereof water. The precipitated dyestufi is filtered off by only one arylamine group is introduced into and washed with water until the red-blue wash the naphthazarine intermediate, new compounds turns to blue-green. The precipitate is then 55 This invention relates to the preparation of new and valuable compounds of the naphthalene series.

It is known that when dim'tro-naphthalene is are obtained which although less soluble in petroleum oil distillates have good affinity for cellulose acetate, and exhibit good fastness properties when applied to that material.

dried It dyes cellulose acetate in bright greenish blue shades of excellent fastness to light.

Other amines of the benzene series may be used to prepare products having the capacity to dye cellulose acetate to a greater or smaller degree. Amongthese; may bementioned aniline, o-phenetidine; p-aminoacetanilide, p-aminodimethyl-aniline, m-toluidine, etc.

These colors may be'appiied to cellulose acetate and related materials by suspending them in an aqueous dye bath from which they are directly absorbed by such materials. The following example is given to illustrate-a common method 7 for applying such colors to-cellulose acetate fibers.

3 parts of the dry powdered color are milled with 12 parts of a solution of the condensation product of beta-naphthalenesulfonic acid and formaldehyde in 15 parts-.otw'ater. This paste is then added to an aqueous soap solution from which the fiber is dyed at temperatures preferably from to C.

We claim:

1. As new compounds, the condensation products of. equal molecular quantities of naphthazarine intermediate and an amine of the benzene series.

2. As a new compound, the condensation prod uct of equalmolecul'ar quantities of naphthazarine intermediate and p-aminophenol.

*3. The process which comprises reacting naphthazarine intermediate in an organic solvent for the same with an equal molecular quantity of an aromatic amine by heating at a temperature of C. and above.

4. Cellulose acetate dyed with the product of claim 1. 

